EP3350239B1 - Bitumen-/polymerzusammensetzung mit verbesserten mechanischen eigenschaften - Google Patents

Bitumen-/polymerzusammensetzung mit verbesserten mechanischen eigenschaften Download PDF

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Publication number
EP3350239B1
EP3350239B1 EP16777727.5A EP16777727A EP3350239B1 EP 3350239 B1 EP3350239 B1 EP 3350239B1 EP 16777727 A EP16777727 A EP 16777727A EP 3350239 B1 EP3350239 B1 EP 3350239B1
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Prior art keywords
weight
bitumen
monomer
block
ethylene
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French (fr)
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EP3350239A1 (de
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Carole RUOT
Romuald Botel
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TotalEnergies Marketing Services SA
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Total Marketing Services SA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/20—Mixtures of bitumen and aggregate defined by their production temperatures, e.g. production of asphalt for road or pavement applications
    • C08L2555/22—Asphalt produced above 140°C, e.g. hot melt asphalt
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
    • C08L2555/80—Macromolecular constituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2555/00—Characteristics of bituminous mixtures
    • C08L2555/40—Mixtures based upon bitumen or asphalt containing functional additives
    • C08L2555/80—Macromolecular constituents
    • C08L2555/84—Polymers comprising styrene, e.g., polystyrene, styrene-diene copolymers or styrene-butadiene-styrene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to the field of bitumens. More specifically, it relates to thermally crosslinkable bitumen / polymer compositions comprising an olefinic polymer type adjuvant, these compositions having improved mechanical properties.
  • the invention also relates to the use of these compositions in the fields of road applications such as hot mixes; warm mixes; cold mixes, for example cold mixes or severe emulsions; or surface coatings, for example emulsions or fluxed bitumens; and in the fields of industrial applications, for example in the manufacture of interior and exterior coatings.
  • bituminous compositions having improved properties and their method of preparation have been widely described in the literature.
  • the random or block copolymers of styrene and of a conjugated diene and, in particular, styrene and butadiene or styrene and isoprene are known to be particularly effective because they mix very easily in the bitumens and give them excellent mechanical properties and in particular very good elastic properties.
  • bitumen / polymer compositions are used for the preparation of binders for various surface coatings and, in particular, as road surface coatings, provided that these compositions have in combination a number of mechanical properties. Optimized mechanical characteristics such as elastic properties are particularly crucial for applications in road surfaces.
  • bitumen / polymer compositions containing a bitumen or a mixture of bitumens and 0.3% to 20%, by weight relative to the weight of bitumen, of at least one primary polymer chosen from certain elastomers and plastomers and 0.01% at 12% by weight of at least one olefin polymer-type adjuvant carrying epoxy or COOH groups.
  • the polymers used in this document are different from those of the invention.
  • the role of the adjuvant is to avoid the demixing between the bituminous phase and the polymer phase, which improves the storage stability of the composition.
  • compositions are sulfur crosslinked and employ an SBS block terpolymer.
  • WO2008 / 137394 discloses a process for preparing a polymer modified bituminous binder composition in the absence of crosslinking agents by heating bitumen at a temperature of 160 ° C to 221 ° C, adding a block copolymer composition and stirring to form a homogeneous mixture.
  • the block copolymer compositions used comprise one or more block copolymers having at least one monovinylaromatic block, at least one polybutadiene block having a vinyl content of less than 15 mol percent and at least one polybutadiene block having a vinyl content of more than 25 percent by mole. It is taught that the bitumen / polymer compositions thus formulated have improved mechanical properties, such as ductility, and good storage stability.
  • the object of the invention is to develop an additive bitumen composition which is thermally crosslinkable and which has improved elastic properties and storage stability.
  • the ratio by mass: S-B1-B2 / (S-B1-B2) nX is greater than or equal to 1: 1, preferably 1: 1 to 10: 1, and most preferably 1: 1 to 4: 1.
  • S represents styrene
  • the composition comprises from 0.5% to 20% by weight of elastomer relative to the total mass of the composition, preferably from 0.5 to 15%.
  • the composition comprises from 0.05% to 2.5% by weight of olefinic polymer adjuvant relative to the total mass of the composition, preferably from 0.15 to 2%.
  • the olefinic polymer adjuvant is chosen from random or block terpolymers of ethylene, of a monomer A chosen from vinyl acetate and C 1 -C 6 alkyl acrylates or methacrylates. and a monomer B selected from glycidyl acrylate and glycidyl methacrylate, comprising from 0.5% to 40% by weight of units derived from monomer A and from 0.5% to 15% by weight of units from the monomer B, the rest being formed from units derived from ethylene.
  • the olefinic polymer adjuvant is chosen from the random terpolymers of ethylene, a monomer A chosen from C 1 to C 6 alkyl acrylates or methacrylates and a monomer B selected from glycidyl acrylate and glycidyl methacrylate, comprising from 0.5% to 40% by weight of units derived from monomer A and from 0.5% to 15% by weight of units derived from monomer B, the remainder being formed from patterns derived from ethylene.
  • the invention also relates to an asphalt characterized in that it comprises at least one bitumen / polymer composition as defined above, and mineral and / or synthetic fillers.
  • the invention also relates to an asphalt characterized in that it consists essentially of at least one bitumen / polymer composition as defined above, and mineral and / or synthetic fillers.
  • the invention also relates to a bituminous mix characterized in that it comprises at least one bitumen / polymer composition as defined above, aggregates, and optionally mineral and / or synthetic fillers.
  • the invention also relates to a bituminous mix characterized in that it consists essentially of at least one bitumen / polymer composition as defined above, aggregates, and optionally mineral and / or synthetic fillers.
  • the invention also relates to the use of at least one bitumen / polymer composition as defined above for preparing a surface coating, a hot mix, a warm mix, a cold mix, a cold mix, a cold mix, a a serious emulsion, said binder being associated with aggregates and / or recycling costs.
  • the invention also relates to the use of at least one bitumen / polymer composition as defined above, for preparing a sealing coating, a membrane or an impregnation layer.
  • compositions of the invention have many advantages: they have improved elastic properties, in particular an improved tensile strength, in particular a traction at 5 ° C. measured according to EN 13587 greater than or equal to 500%. They also exhibit a satisfactory stability in hot storage, in particular a storage stability at 180 ° C. of greater than or equal to 3 days, in particular a storage stability at 180 ° C. characterized by a variation in penetrability at 25 ° C., measured according to US Pat. standard EN 1426 less than or equal to 5 1/10 mm and / or a ball and ring temperature variation measured according to standard 1427 less than or equal to 5 ° C.
  • the combination of elastomer and olefinic polymer adjuvant developed makes it possible to improve the mechanical properties, in particular the elastic properties, and the storage stability of a wide range of bitumen compositions.
  • the Applicant has discovered that the use of a specific elastomer in combination with a particular polymer adjuvant for the preparation of bitumen / polymer compositions makes it possible to improve surprisingly the mechanical properties, in particular the elastic properties, in particular the resistance to traction, and storage stability of this bitumen / polymer composition. Indeed, the Applicant has demonstrated a particular synergistic effect induced by the joint use of a particular elastomer and a specific polymer adjuvant. This observation is not limited to a particular class of bitumen.
  • bitumen / polymer composition of the invention has the advantage of being economical with respect to a bitumen / polymer composition based on the same block polymers S-B1-B2 and without adjuvant.
  • the addition of the adjuvant, in small quantities makes it possible to significantly reduce the amount of block polymer used. work, with equivalent mechanical properties, or even higher and provides a very satisfactory storage stability.
  • bitumen / polymer composition and “bitumen / polymer binder” represent the same type of composition and are used interchangeably.
  • the invention relates to bitumens. These can be formed by one or more bitumen bases.
  • bitumen any bituminous compositions consisting of one or more bitumen bases and possibly comprising one or more chemical additives, said compositions being intended for a road application or an industrial application.
  • bitumen bases that may be used according to the invention, mention may first be made of bitumens of natural origin, those contained in deposits of natural bitumen, natural asphalt or bituminous sands and bitumens originating from the refining of crude oil. .
  • the bitumen bases according to the invention are advantageously chosen from bitumen bases originating from the refining of crude oil.
  • the bitumen bases may be chosen from bitumen bases or bitumen base mixtures derived from the refining of crude oil, in particular bitumen bases containing asphaltenes or pitches.
  • the bitumen bases can be obtained by conventional processes for the manufacture of bitumen bases in a refinery, in particular by direct distillation and / or vacuum distillation of the oil.
  • bitumen bases may optionally be visbroken and / or deasphalted and / or rectified in air.
  • Vacuum distillation of atmospheric residues from atmospheric distillation of crude oil is common. This manufacturing process therefore corresponds to the succession of an atmospheric distillation and a distillation under vacuum, the feed supplying the vacuum distillation corresponding to the atmospheric residues.
  • These vacuum residues from the vacuum distillation tower can also be used as bitumens. It is also common to inject air into a compound charge usually distillates and heavy products from the vacuum distillation of atmospheric residues from the distillation of petroleum. This method provides a base blown, or semi-blown or oxidized or rectified in air or rectified partially in air.
  • bitumen bases obtained by the refining processes can be combined with each other to obtain the best technical compromise.
  • the bitumen base can also be a bitumen base for recycling.
  • the bitumen bases may be bitumen bases of hard grade or soft grade.
  • production temperatures of between 100 ° C. and 200 ° C., preferably between 140 ° C. and 200 ° C., are used, and stirring is carried out for a period of time. at least 10 minutes, preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours.
  • the term "manufacturing temperature” means the heating temperature of the bitumen base (s) before mixing as well as the mixing temperature. The temperature and the duration of the heating vary according to the quantity of bitumen used and are defined by the standard NF EN 12594.
  • the blown bitumens can be manufactured in a blowing unit, by passing a stream of air and / or oxygen through a starting bituminous base.
  • This operation can be carried out in the presence of an oxidation catalyst, for example phosphoric acid.
  • the blowing is carried out at high temperatures, of the order of 200 to 300 ° C, for relatively long periods of time typically between 30 minutes and 2 hours, continuously or in batches. The duration and the blowing temperature are adjusted according to the properties targeted for the blown bitumen and according to the quality of the starting bitumen.
  • Bitumen can also be a recycling bitumen.
  • the bitumens may be hard grade or soft grade bitumens.
  • the bitumens which can be used according to the invention have a penetrability, measured at 25 ° C. according to the EN 1426 standard, of from 5 to 330 1/10 mm, preferably from 10 to 220 1/10 mm, more preferably from 10 to 120 1 / 10 mm.
  • the so-called “needle penetration” measurement is carried out by means of a standardized test NF EN 1426 at 25 ° C. (P 25 ). This characteristic of penetrability is expressed in tenths of a millimeter (dmm or 1/10 mm).
  • the needle penetration, measured at 25 ° C, according to the standardized test NF EN 1426, represents the measurement of the penetration into a sample of bitumen, after a time of 5 seconds, a needle whose weight with its support is 100 g.
  • the NF EN 1426 standard replaces the homologated NF T 66-004 standard of December 1986 with effect from December 20, 1999 (decision of the Chief Executive Officer of AFNOR dated November 20, 1999).
  • the monomer A is chosen from vinyl acetate and C 1 -C 6 alkyl acrylates or methacrylates.
  • Monomer B is selected from glycidyl acrylate and glycidyl methacrylate.
  • the olefinic polymer adjuvant is preferably selected from the terpolymers (b) ethylene / monomer A / monomer B described above and from mixtures (d) comprising them.
  • the olefinic polymer adjuvant is advantageously chosen from the terpolymers (b) ethylene / monomer A / monomer B described above and from the mixtures (d) in which the terpolymers (b) represent at least 50% by weight relative to to the total mass of the mixture, preferably at least 75% by weight, more preferably at least 90% by weight.
  • the olefinic polymer adjuvant is chosen from among the random terpolymers of ethylene, a monomer A chosen from C 1 to C 6 alkyl acrylates or methacrylates and a monomer B chosen from glycidyl acrylate. and glycidyl methacrylate, comprising from 0.5% to 40% by weight, preferably from 5% to 35% by weight, more preferably from 10% to 30% by weight of units derived from monomer A and 0.5% by weight at 15% by weight, preferably from 2.5% to 15% by weight of units derived from monomer B, the remainder being formed from units derived from ethylene.
  • the elastomer is a tri-block copolymer or a mixture of tri-block copolymers.
  • thermally crosslinkable block copolymers of formula S-B1-B2 in which S represents a monovinyl aromatic hydrocarbon block having a peak molecular weight of 10,000 to 25,000, B1 is a polybutadiene block having a vinyl content less than or equal to 15 mol percent, B2 is a polybutadiene block having a vinyl content greater than or equal to 25 mole percent, and the mass ratio B1 / B2 is greater than or equal to 1: 1, and wherein the block terpolymer is S-B1-B2 has a peak molecular weight of from about 40,000 to about 200,000.
  • S represents a monovinyl aromatic hydrocarbon block having a peak molecular weight of 10,000 to 25,000
  • B1 is a polybutadiene block having a vinyl content less than or equal to 15 mol percent
  • B2 is a polybutadiene block having a vinyl content greater than or equal to 25 mole percent
  • the mass ratio B1 / B2 is greater than or equal to 1:
  • the elastomer may further comprise at least one thermally crosslinkable block copolymer having the formula (S-B1-B2) nX wherein each S represents a monovinyl aromatic hydrocarbon block having a peak molecular weight of 10,000 to 25,000, each B1 represents a polybutadiene block having a content in vinyl less than or equal to 15 mole percent, each B2 is a polybutadiene block having a vinyl content greater than or equal to 25 mole percent, n is an integer of 2 to 6, and X is the residue of a coupling agent, the mass ratio B1 / B2 is greater than or equal to 1: 1, and the block copolymer (S-B1-B2) nX has a peak molecular weight which is 1.5 to 6.0 times the peak molecular weight of the S-B1-B2 block copolymer.
  • S represents a monovinyl aromatic hydrocarbon block having a peak molecular weight of 10,000 to 25,000
  • each B1 represents a polybutadiene
  • the monovinylaromatic hydrocarbon groups designated S can be any monovinylaromatic hydrocarbon compound known for use in the preparation of block copolymers such as: styrene, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2, 4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene or mixtures thereof.
  • the preferred monovinyl aromatic hydrocarbon compound according to the present invention is styrene, which is used as a substantially pure monomer or as a major component in mixtures with minor proportions of another structurally related vinyl aromatic monomer, such as o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, alpha-methylstyrene, vinylnaphthalene, vinyltoluene and vinylxylene, namely, in proportions of at most 10% in weight.
  • the use of substantially pure styrene is particularly preferred in the present invention.
  • the polybutadiene blocks B1, B2 used in the above-mentioned block copolymers are based on substantially pure butadiene monomer or comprising minor proportions, up to 10% by weight, of structurally related conjugated dienes.
  • the polybutadiene is purely constituted from butadiene monomer.
  • the term "molecular weight” refers to the true molecular weight in g / mol of the block copolymer.
  • the molecular weights mentioned in the specification and claims can be measured by gel permeation chromatography (GPC) using polystyrene standards, for example as taught by ASTM 3536.
  • GPC gel permeation chromatography
  • polystyrene standards for example as taught by ASTM 3536.
  • GPC is a well-known process in which polymers are separated according to their molecular mass, the largest molecule being eluted first.
  • the chromatograph is calibrated using polystyrene standards of various molecular weights available commercially.
  • the molecular weight of the polymers measured by GPC is a molecular weight equivalent of styrene.
  • the styrene equivalent molecular weight can be converted to a true molecular weight when the styrene content of the polymer and the vinyl content of the diene blocks are known.
  • the detector used is preferably a combination of ultraviolet rays and a detector of refraction. Molecular weights are measured at the peak of the GPC peak, converted to true molecular weights, and are commonly referred to as peak molecular weights.
  • each monovinyl aromatic hydrocarbon block is from about 10,000 to about 25,000, preferably from about 12,000 to about 20,000. According to a preferred variant, the peak molecular weight of styrenic blocks range from about 14,000 to about 18,000.
  • Each block copolymer of the formula S-B1-B2 used in the present invention has a peak molecular weight of about 40,000 to about 200,000, preferably about 65,000 to about 160,000, more preferably about 75,000. 000 to about 150,000, and still more preferably from about 75,000 to 130,000.
  • the peak molecular weight of the block copolymers of formula (S-B1-B2) nX depends on the peak molecular weight of the block copolymer of formula S-B1-B2 used. More specifically, the peak molecular weight of the (S-B1-B2) nX copolymers is from about 1.5 to about 6.0 times the peak molecular weight of the S-B1-B2 block copolymer. Preferably, the peak molecular weight of the (S-B1-B2) nX block copolymers is from about 1.8 to about 5.0 times the peak molecular weight of the S-B1-B2 block copolymer.
  • the combined molecular weight of the two butadiene blocks (B1 and B2) is from about 25,000 to about 190,000.
  • the two butadiene blocks (B1 and B2) are present in a weight ratio B1 / B2 greater than or equal to 1: 1.
  • B1 is present in an amount (% by weight) greater than or equal to 50% of the total of segment B1-B2
  • B2 is present in an amount (% by weight) less than or equal to 50% of the total of segment B1-B2.
  • the polybutadiene block B1 it is preferred that there be at most about 15 mole percent of vinyl in block B1.
  • the vinyl content in the B1 block should be from about 5 mole percent to about 15 mole percent of the fused polybutadiene units.
  • the known anionic polymerization processes of butadiene typically from about 7 to about 15 mole percent of the polybutadiene units have the 1,2-addition configuration.
  • the vinyl content in the B2 block is from about 25 mole percent to about 80 mole percent of the fused polybutadiene units, more preferably about 40 mole percent to about 75 mole percent of the polybutadiene units have a 1,2-addition configuration. and even more preferably from about 50 to about 65 mole percent of the polybutadiene units have a 1,2-addition configuration.
  • the content of monovinyl aromatic hydrocarbon monomer of the copolymer is from about 10% to about 40% by weight, based on the total weight of the block copolymer S-B1-B2 and optionally (S-B1 -B2) n.
  • the monovinyl aromatic hydrocarbon content (preferably styrene) of the S-B1-B2 block copolymers, and optionally (S-B1-B2) nX is from about 18% to about 35% by weight, more preferably from from about 19% to about 32% by weight, based on the total weight of the copolymer.
  • the elastomer comprises a block copolymer of the formula S-B1-B2 alone.
  • S-B1-B2 is used in combination with a block copolymer of formula (S-B1-B2) nX wherein each S is a monovinyl aromatic hydrocarbon block, preferably styrene, each B1 is a polybutadiene block having a vinyl content of less than or equal to 15 mole percent, each B2 is a polybutadiene block having a vinyl content greater than or equal to 25 mole percent, n is an integer ranging from 2 to And X is the residue of a coupling agent.
  • the block copolymers of the invention are in a substantially non-hydrogenated form.
  • the mass ratio of the S-B1-B2 / (S-B1-B2) nX block copolymer is greater than or equal to about 1: 1.
  • the ratio is from about 1: 1 to about 10: 1, with the preferred ratio being from about 1: 1 to about 4: 1.
  • the weight average molecular weight of the elastomer is advantageously between 10,000 and 600,000 daltons, preferably between 30,000 and 400,000 daltons.
  • the block copolymers used in the invention are described in WO2008 / 137394 .
  • a process for their preparation is described in the documents US 3231635 ; US 3251905 ; US 3390207 ; US 3598887 ; US 4219627 ; EP0413294 ; EP0387671 ; EP 0636654 and WO 94/22931 .
  • composition may comprise other elastomers than S-B1-B2 block terpolymers and (S-B1-B2) nX copolymers.
  • composition according to the invention may contain other known bitumen elastomers such as copolymers SB (block copolymer of styrene and butadiene), SBS (styrene-butadiene-styrene block copolymer), SIS (styrene-isoprene).
  • SB block copolymer of styrene and butadiene
  • SBS styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene
  • SBS * styrene-butadiene-styrene star block copolymer
  • SBR styrene-b-butadiene rubber
  • EPDM modified ethylene propylene diene
  • polychloroprene polynorbornene, natural rubber, recycled rubber, polybutene, polyisobutylene
  • SEBS copolymer of styrene, ethylene, butylene and styrene.
  • the block terpolymers S-B1-B2 and the copolymers (S-B1-B2) nX represent at least 50% by weight of the elastomers present in the composition, still more preferably at least 70% in mass.
  • the elastomer consists essentially of S-B1-B2 block terpolymers and nX (S-B1-B2) block copolymers.
  • the molecular weight of the copolymer is measured by GPC chromatography with a polystyrene standard according to ASTM D5296-05.
  • composition may further comprise plastomers.
  • composition according to the invention may also contain one or more polymeric components chosen from the category of known bitumen plastomers such as polyethylene PE (polyethylene), HDPE (high density polyethylene), polypropylene PP, EVA (polyethylene copolymer). vinyl acetate), EMA (polyethylene-methyl acrylate copolymer), copolymers of olefins and unsaturated carboxylic esters, EBA (polyethylene-butyl acrylate copolymer), copolymers of ethylene and of acid esters acrylic, methacrylic or maleic anhydride, ethylene-propylene copolymers, ABS (acrylonitrile-butadiene-styrene).
  • bitumen plastomers such as polyethylene PE (polyethylene), HDPE (high density polyethylene), polypropylene PP, EVA (polyethylene copolymer). vinyl acetate), EMA (polyethylene-methyl acrylate copolymer), copolymers of olefins
  • the composition according to the invention comprises at least one plastomer as defined above
  • the S-B1-B2 block terpolymers and the copolymers (S-B1-B2) nX represent at least 50% by weight relative to the total mass of all of the S-B1-B2 block terpolymers, nX (S-B1-B2) copolymers and plastomeres present in the composition more preferably at least 70% by weight.
  • the composition may further comprise S-B1-B2 block terpolymers and (S-B1-B2) nX copolymers, at least one other elastomer as defined above and at least one plastomer as defined above.
  • the block terpolymers S-B1-B2 and the copolymers (S- B1-B2) nX represent at least 50% by weight relative to the total mass of all the S-B1-B2 block terpolymers, nX (S-B1-B2) copolymers, elastomers and plastomeres present in the composition, still more preferably at least 70% by weight.
  • paraffins may also contain a large proportion of so-called "normal" paraffins, that is, straight-chain, unbranched linear paraffins (saturated hydrocarbons).
  • paraffins can comprise from 50 to 100% of normal paraffins and from 0 to 50% of isoparaffins and / or branched paraffins.
  • the paraffins comprise 85 to 95% of normal paraffins and 5 to 15% of isoparaffins and / or branched paraffins.
  • the paraffins comprise from 50 to 100% of normal paraffins and from 0 to 50% of isoparaffins.
  • the paraffins comprise from 85 to 95% of normal paraffins and from 5 to 15% of isoparaffins.
  • the paraffins are paraffins of polymethylene. More particularly, paraffins are synthetic paraffins of polymethylene, especially paraffins resulting from the conversion of synthesis gas by the Fischer-Tropsch process. In the Fischer-Tropsch process, paraffins are obtained by reaction of hydrogen with carbon monoxide on a metal catalyst. Fischer-Tropsch synthesis methods are described, for example, in the publications EP 1 432 778 , EP 1 328 607 or EP 0 199 475 .
  • the additives are used according to the amounts well known to those skilled in the art, depending on the nature of the additive, depending on the bitumen base and the expected properties.
  • the bitumen base comprises from 0.1% to 10% by weight, preferably from 0.5% to 5% by weight, more preferably from 0.5% to 2.5% by weight. mass of chemical additive in relation to the total mass of the bitumen base.
  • composition The composition :
  • the percentages by weight are calculated with respect to the total mass of said composition.
  • the elastomer mass / olefinic polymer builder ratio is advantageously from 15/1 to 2/1, preferably from 12/1 to 5/2.
  • bitumen / polymer compositions of the invention may be prepared by any method known to those skilled in the art. Typically these processes include mixing the components and heating the mixture. The bitumen can be heated before mixing. Usually, the bitumen is heated before mixing, and the other components are added to the bitumen without having been previously heated.
  • the percentages by weight are calculated with respect to the total mass of said composition.
  • It operates at temperatures ranging from 100 ° C to 200 ° C, preferably from 150 ° C to 200 ° C, more preferably from 160 ° C to 200 ° C, and with stirring for a period of at least 10 minutes, preferably from 1 hour to 24 hours, more preferably from 1 hour to 10 hours.
  • the process of the invention can be carried out by means of agitation producing high shear or low shear agitation.
  • the process of the invention may comprise successive sequences with different modes of agitation, for example the process of the invention may comprise at least two successive stirring sequences, a first sequence producing high shear agitation followed by a second sequence producing low shear agitation.
  • the olefinic polymer adjuvant may be incorporated into the bitumen before or after the thermally crosslinkable elastomer, simultaneous incorporation may also be envisaged.
  • the olefinic polymer adjuvant is incorporated into the bitumen before or after the elastomer.
  • the olefinic polymer adjuvant and the elastomer are incorporated in the bitumen.
  • the stirring at high shear and in particular the stirring performed by passing through a high shear mill, facilitates the good dispersion and good distribution of the polymer and the olefinic polymer adjuvant.
  • bitumen / polymer compositions obtained according to the invention are envisaged.
  • the bitumen / polymer compositions may be used for the preparation of a bitumen / polymer binder.
  • the bitumen / polymer binder according to the invention can be used in combination with aggregates, especially road aggregates.
  • the invention relates in particular to bituminous mixes as materials for the construction and maintenance of roadway bodies and their pavement, as well as for carrying out all road works.
  • Asphalt mix means a mixture of a bituminous binder with aggregates and optionally mineral and / or synthetic fillers.
  • the bituminous mix comprises a bitumen / polymer binder according to the invention, and optionally mineral and / or synthetic fillers, preferably chosen from fines, sand, chippings and recycling costs.
  • the aggregates are inorganic and / or synthetic aggregates, in particular, recycling costs, of dimensions greater than 2 mm, preferably of between 2 mm and 20 mm.
  • bitumen / polymer binder according to the invention may advantageously be used to prepare a surface coating, a hot mix, a warm mix, a cold mix, a cold mix or a serious emulsion.
  • the invention also relates to asphalts as materials for manufacturing and covering sidewalks.
  • asphalt is meant a mixture of bituminous binder with mineral and / or synthetic fillers.
  • An asphalt comprises a bitumen / polymer binder according to the invention and mineral fillers such as fines, sand or chippings and / or synthetic fillers.
  • the mineral fillers consist of fines (particles smaller than 0.063 mm), sand (particles with dimensions of between 0.063 mm and 2 mm) and possibly chippings (particles with dimensions larger than 2 mm, preferably between 2 mm and 4 mm).
  • Asphalts are 100% compact and are mainly used to make and cover sidewalks, while asphalt mixes have a compactness of less than 100% and are used to make roads. Unlike asphalt, asphalt is not compacted with a roller when it is put in place.
  • bitumen / polymer composition in various industrial applications, in particular for preparing a sealing coating, a membrane or an impregnation layer.
  • bituminous compositions As regards the industrial applications of the bituminous compositions according to the invention, mention may be made of the manufacture of waterproofing membranes, noise barriers, insulation membranes, surface coatings, carpet tiles, impregnation layers .
  • the subject of the invention is also the use of bitumen / polymer binders, asphalt mixes and cast asphalts according to the invention for the manufacture of road, pavement, sidewalk, road and urban pavement coverings. , floors, waterproofing of buildings or structures, in particular for the manufacture in road application, foundation layers, base layers, bedding layers, surface layers such as connecting layers and / or the wearing courses.
  • compositions C1 to C5, C13 and C14 corresponding to the mixtures detailed below in Tables 1 and 1a were prepared with the indicated reaction time.
  • Composition C9 corresponding to the mixture detailed below in Table 1a was prepared with the indicated reaction time.
  • compositions C6 to C8 and C10 to C12 corresponding to the mixtures detailed below in Tables 1 and 1a were prepared with the indicated reaction time.
  • compositions C1, C2, C13 and C14 are comparative, compositions C3 to C12 are according to the invention.
  • Table 1 Prepared compositions C1 to C7 Composition C1 C2 C3 C4 C5 C6 C7 B 97.5 96.5 97.25 96 - - - B1 - - - - 96.72 - - B2 - - - - - 57.15 - B3 - - - - - - 40 40 B4 - - - - - - - 56.62 B5 - - - - - - - B6 - - - - - - - B7 - - - - - - - - E 2.5 3.5 2.5 3 2.85 2.58 2.94 E1 - - - - - - - - adj - - 0.25 1 0.43 0.27 0.44 Reaction time 6
  • the mixture thus obtained is then mixed for 4 hours at a temperature between 185 and 195 ° C.
  • the mixture thus obtained is then mixed for 2 hours at a temperature of 195 ° C.
  • a synergistic effect is observed between the block polymer according to the invention and the olefinic polymer adjuvant, which makes it possible to obtain a very significant improvement in the mechanical properties, in particular of the elastic properties, in particular of traction at 5 ° C., with quantities very weak sequenced polymer / adjuvant system.
  • This synergistic effect between the block polymer and the olefinic polymer adjuvant also makes it possible to obtain a significant improvement in the stability of the hot storage stability, in particular a storage stability at 180 ° C., of the bitumen / polymer composition with very high quantities. weak sequenced polymer / adjuvant system.
  • the combination of the sequenced polymer and the olefinic polymer adjuvant according to the invention makes it possible to obtain a very significant improvement in the mechanical properties, in particular of the elastic properties, in particular. Particularly tensile at 5 ° C, with very small amounts of block polymer / adjuvant system.
  • An asphalt mix (EB1) is respectively obtained from the composition C16 according to the invention and granules having the granular section described in Table 3: Table 3: Granulometric Composition Cup (mm) 0/2 2/4 4/6 6/10 filler Weight (%) 39 10 12 38 1
  • bituminous mix thus obtained has a C16 bituminous composition content of 5.7% by mass relative to the total mass of the bituminous mix.
  • An asphalt concrete is characterized as a high modulus asphalt concrete for wearing course or type EB 10 bond, also called BBME class 3 according to standard NF EN 13108-1, if it has at least the following characteristics described in the table 4: Table 4: Mechanical Properties of Asphalt (EB1) EB1 coated BBME class 3 specifications according to EN 13108-1 Duriez test at 18 ° C (1) (r / R) 0.89 ⁇ 0.8 Rutting test at 30,000 cycles (%) (2) 1.7 ⁇ 5 Complex module test at 15 ° C and 10Hz (MPa) (3) 11,500 ⁇ 11,000 Fatigue test ( ⁇ def for 10 6 cycles) (4) 199 ⁇ 100 (1) Water stripping resistance test according to EN 12697-12, reflecting the adhesion between the bitumen / polymer composition and the aggregates.
  • Table 4 Mechanical Properties of Asphalt (EB1) EB1 coated BBME class 3 specifications according to EN 13108-1 Duriez test at 18 ° C (1) (r / R) 0.89 ⁇ 0.8 Rutting test at 30,000 cycles (%) (2) 1.7
  • bituminous mix EB1 obtained from the composition C16 according to the invention has mechanical properties fulfilling the conditions of use of this mix as BBME class 3 for the production of wearing courses or binding subjected to high stresses of traffic

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Claims (13)

  1. Bitumen-/Polymerzusammensetzung, umfassend:
    - Bitumen,
    - mindestens ein Elastomer, und
    - mindestens ein Olefinpolymer-Adjuvans, das mindestens mit funktionellen Glycidylgruppen funktionalisiert ist,
    dadurch gekennzeichnet, dass
    • das Elastomer ausgewählt ist aus thermovernetzbaren Blockcopolymeren mit der Formel S-B1-B2, wobei S einen aromatischen Monovinylkohlenwasserstoffblock mit einem maximalen Molekulargewicht von 10 000 bis 25 000 darstellt, B1 ein Polybutadienblock mit einem Vinylgehalt kleiner oder gleich 15 Molprozent ist, B2 ein Polybutadienblock mit einem Vinylgehalt größer oder gleich 25 Molprozent ist, das Massenverhältnis B1/B2 größer oder gleich 1:1 ist, und wobei das Blockcopolymer S-B1-B2 ein maximales Molekulargewicht von 40 000 bis 200 000 aufweist;
    • das Elastomer außerdem mindestens ein thermovernetzbares Blockcopolymer mit der Formel (S-B1-B2)nX umfassen kann, wobei jedes S einen aromatischen Monovinylkohlenwasserstoffblock mit einem maximalen Molekulargewicht von 10 000 bis 25 000 darstellt, jedes B1 einen Polybutadienblock mit einem Vinylgehalt kleiner oder gleich 15 Molprozent darstellt, jedes B2 einen Polybutadienblock mit einem Vinylgehalt größer oder gleich 25 Molprozent darstellt, n eine ganze Zahl von 2 bis 6 ist, und X der Rest eines Kopplungsmittels ist, wobei das Massenverhältnis B1/B2 größer oder gleich 1:1 ist, und das Blockcopolymer (S-B1-B2)nX ein maximales Molekulargewicht aufweist, welches das 1,5- bis 6,0-fache des maximalen Molekulargewichts des Blockcopolymers S-B1-B2 beträgt;
    und das Massenverhältnis Elastomer/Adjuvans in der Zusammensetzung von 15/1 bis 2/1 beträgt.
  2. Zusammensetzung nach Anspruch 1,
    wobei das Massenverhältnis:

            S-B1-B2/(S-B1-B2)nX

    größer oder gleich 1:1 ist, vorzugsweise von 1:1 bis 10:1 und noch besser von 1:1 bis 4:1.
  3. Zusammensetzung nach Anspruch 1 oder Anspruch 2,
    wobei S Styrol darstellt.
  4. Zusammensetzung nach einem der vorhergehenden Ansprüche,
    welche von 0,5 Massen-% bis 20 Massen-% Elastomer im Verhältnis zur Gesamtmasse der Zusammensetzung umfasst, vorzugsweise von 0,5 bis 15 %.
  5. Zusammensetzung nach einem der vorhergehenden Ansprüche,
    welche von 0,05 Massen-% bis 2,5 Massen-% Olefinpolymer-Adjuvans im Verhältnis zur Gesamtmasse der Zusammensetzung umfasst, vorzugsweise von 0,15 bis 2 %.
  6. Zusammensetzung nach einem der vorhergehenden Ansprüche,
    wobei das Olefinpolymer-Adjuvans ausgewählt ist aus der Gruppe bestehend aus:
    (a) statistischen oder Blockcopolymeren von Ethylen und einem Monomer, ausgewählt aus Glycidylacrylat und Glycidylmethacrylat, umfassend von 50 Massen-% bis 99,7 Massen-% Ethylen;
    (b) statistischen oder Blockterpolymeren von Ethylen, einem Monomer A, ausgewählt aus Vinylacetat und C1-C6-Alkylacrylaten oder - methacrylaten, und einem Monomer B, ausgewählt aus Glycidylacrylat und Glycidylmethacrylat, umfassend von 0,5 Massen-% bis 40 Massen-% Einheiten, die von dem Monomer A stammen, und von 0,5 Massen-% bis 15 Massen-% Einheiten, die von dem Monomer B stammen, wobei der Rest aus Einheiten gebildet ist, die von Ethylen stammen; und
    (c) Copolymeren, die erhalten werden aus der Pfropfung eines Monomers B, ausgewählt aus Glycidylacrylat und Glycidylmethacrylat, auf ein Substrat, bestehend aus einem Polymer, ausgewählt aus Polyethylenen, Polypropylenen, statistischen oder Blockcopolymeren von Ethylen und Vinylacetat, statistischen oder Blockcopolymeren von Ethylen und C1-C6-Alkylacrylat oder -methacrylat, umfassend von 40 Massen-% bis 99,7 Massen-% Ethylen, wobei die gepfropften Copolymere 0,5 Massen-% bis 15 Massen-% gepfropfte Einheiten umfassen, die von dem Monomer B stammen,
    (d) Mischungen von mindestens zwei Komponenten (a), (b) und (c).
  7. Zusammensetzung nach Anspruch 6,
    wobei das Olefinpolymer-Adjuvans ausgewählt ist aus statistischen oder Blockterpolymeren von Ethylen, einem Monomer A, ausgewählt aus Vinylacetat und C1-C6-Alkylacrylaten oder -methacrylaten, und einem Monomer B, ausgewählt aus Glycidylacrylat und Glycidylmethacrylat, umfassend von 0,5 Massen-% bis 40 Massen-% Einheiten, die von dem Monomer A stammen, und von 0,5 Massen-% bis 15 Massen-% Einheiten, die von dem Monomer B stammen, wobei der Rest aus Einheiten gebildet ist, die von Ethylen stammen.
  8. Zusammensetzung nach Anspruch 7,
    wobei das Olefinpolymer-Adjuvans ausgewählt ist aus statistischen Terpolymeren von Ethylen, einem Monomer A, ausgewählt aus C1-C6-Alkylacrylaten oder -methacrylaten, und einem Monomer B, ausgewählt aus Glycidylacrylat und Glycidylmethacrylat, umfassend von 0,5 Massen-% bis 40 Massen-% Einheiten, die von dem Monomer A stammen, und von 0,5 Massen-% bis 15 Massen-% Einheiten, die von dem Monomer B stammen, wobei der Rest aus Einheiten gebildet ist, die von Ethylen stammen.
  9. Verfahren zur Herstellung einer Bitumen-/Polymerzusammensetzung nach einem der Ansprüche 1 bis 8,
    dadurch gekennzeichnet, dass in Kontakt gebracht werden, wobei bei Temperaturen zwischen 100 °C und 200 °C und unter Rühren während einer Dauer von mindestens 10 Minuten gearbeitet wird:
    - Bitumen,
    - von 0,5 Massen-% bis 20 Massen-% mindestens eines Elastomers,
    - von 0,05 Massen-% bis 2,5 Massen-% mindestens eines Olefinpolymer-Adjuvans,
    - gegebenenfalls Additive.
  10. Asphalt,
    dadurch gekennzeichnet, dass er mindestens eine Bitumen-/Polymerzusammensetzung nach einem der Ansprüche 1 bis 8 und mineralische und/oder synthetische Füllstoffe umfasst.
  11. Bituminöse Beschichtung,
    dadurch gekennzeichnet, dass sie mindestens eine Bitumen-/Polymerzusammensetzung nach einem der Ansprüche 1 bis 8, Granulate und gegebenenfalls mineralische und/oder synthetische Füllstoffe umfasst.
  12. Verwendung mindestens einer Bitumen-/Polymerzusammensetzung nach einem der Ansprüche 1 bis 8, zur Herstellung eines Oberflächenbelags, einer heißen Beschichtung, einer warmen Beschichtung, einer kalten Beschichtung, einer kalt gegossenen Beschichtung, einer schweren Emulsion, wobei das Bindemittel mit Granulaten und/oder gemahlenem wiederverwendetem Material assoziiert ist.
  13. Verwendung mindestens einer Bitumen-/Polymerzusammensetzung nach einem der Ansprüche 1 bis 8, zur Herstellung einer Dichtungsbeschichtung, einer Membran oder einer Imprägnierungsschicht.
EP16777727.5A 2015-09-18 2016-09-15 Bitumen-/polymerzusammensetzung mit verbesserten mechanischen eigenschaften Active EP3350239B1 (de)

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RU2018112942A (ru) 2019-10-18
AR106045A1 (es) 2017-12-06
PL3350239T3 (pl) 2020-05-18
WO2017046523A1 (fr) 2017-03-23
EP3350239A1 (de) 2018-07-25
US10597535B2 (en) 2020-03-24
RU2018112942A3 (de) 2019-12-13
FR3041355B1 (fr) 2017-09-01
FR3041355A1 (fr) 2017-03-24
US20180244920A1 (en) 2018-08-30

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